Extraction of Cu(II), Ni(II), and Co(II) metal ions from aqueous solutions was investigated using iminobis(N‐2‐aminoethylacetamide) polysiloxane‐immobilized ligand system of the general formula P‐(CH2)3‐N(CH2CONHCH2CH2NH2)2, where P represents [Si‐O]n siloxane network. The immobilized ligand system also showed high selectivity to separate copper(II) from a mixture of metal ions (Co(II), Ni(II), Cu(II)) when used as chromatographic stationary phase. The ligand system preconcentrated Cu(II) effectively at different concentrations when used as a stationary phase extractant. The optimum pH for maximum metal uptake appeared to be pH 5.0 using acetate buffer solution. The preconcentated chemisorbed metal ions were regenerated from the solid extractant using 0.5 M HCl.